Azo dyesiuffs and their production



Patented Sept. 8, 1936 Azo DYESTUFFS'AND 'r'nsmrnonuo'rlo Detlef Delis,

Leverkusen-i. GFWQIk, Germany,

assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware I No Drawing. Application March 11, 1935, Serial No. 10,522. In Germany March 17, 1934 9 Claims.

I Thepresent invention relates to a process of preparing azodyestuffs and the new products 010- tainable by the said process, more particularly it relates to a process of preparing azodyestufiscontaming at least once the grouping SOaH H ethoxy; aryl, suchas phenyl; aralkyl, such as a the nitro groupand radical of the benzyl series;

the like. 7 g

In accordance with the present invention a'zo dyestuffs of the above-identified general formula are prepared by starting with an azodyestuff containing at least once the grouping halogen y .11 V wherein R1 and R2 standfor radicals of the benzene or naphthalene series, and reacting upon the same with a watersoluble. sulfite in the presence of an agent yielding copper in an aqueous neutral to alkaline medium at elevated temperature. I I

As agents" yielding copper there may be used finely divided copper or copper compounds generally used in the art of preparing copper complex compounds of azodyestuffs, for instance, copper oxide or hydroxide, copper salts, such as cupric sulfate and cupric chloride, further, the complex compounds of copper with tertiary organic bases, for example, the complex compound of cupric sulfate with pyridine, or finally the copper complex compounds of organic hydroxy compounds, for instance, of glycerine or tartaric acid.

The quantity of the copper compound used for performing my new process may be varied within wide limits. The reaction probably proceeds in such a manner that in a first step the starting dyestuff yields a copper complex compound in which the halogen atom can easily be substituted by other substituents, in the present case, by a sulfonic acid group. As the copper complex compound of the o-sulfo-o'-hydroxy-azodyestuff is rather unstable, the copper tends to split off, and

for this reason, it is not necessary to use equimolecular quantities of the starting dyestuff and of the copper compound, because the copper split off from the o-sulfo-o-hydroxyazodyestuif complex compound can enter intoreaction with unchanged starting dyestuff eventually present.

As outlined above the reaction is performed in a neutral or alkaline "aqueous medium; however, it shall be mentioned that a caustic alkaline reac: tion advantageously is avoided in view of the tendency of the halogen to be substituted by the hydroxygro-upin a caustic alkaline medium.

The-process may be performed attemperatures between about '70 and about C., however, I WlShll/tO be understood that the same can. also be, performed at temperatures beyond the limits given without departing from the spirit of my invention,-f or, example, the reaction may be carried out at higher temperatures and with the application of pressure. p a

By the presence of'nitrogen containing tertiary bases. such as pyridine, the reaction is accelerated in many cases, and the addition of such bases is of especial value when waterinsoluble azodyestuffs are used as starting components, in this case the base simultaneously acting as solvent. a

When separating the reaction products from an alkaline medium they may contain copper in a complex form which copper may be removed by treating with an acid. r a e The invention is illustrated by the following examples,

Example 1.50 grams of the azcdyestuff from diazotized 3 amino 4 chlor l-methylbenzene and 2-hydroxynapthalene-5, 'l-disulfonic acid are dissolved in 1000 cos. of' hot water. To the solution there are added 5 grains of crystallized copper sulfate, and after the same have dissolve'd 15 grams of calcined "sodium carbonate. The solution is then heated to90 perature 20 grams of sodium sulfite free from water are added. After stirring for 3 hours, the new dyestuff is isolated in the usual manner; it is soluble in water with an orange coloration. In the free state it corresponds to the following formula:

s 03H on Q SOzH When substituting the 3-amino-4-chloro-1- PATENT OFFICE f without being limited thereto: I

0., and at this temmethylbenzene by the 2 amino 3 chloro 1- methylbenzene or by o-chloroaniline and the 2- hydroxynaphhalene-5, 7-disulfonic acid by 2- naphthol-G-sulfonic acid, 2 naphthol-3,6-disulfonic acid or 2-amino-8-naphthol-6-sulfonic acid or an N-acyl derivative thereof, the process proceeds in the same manner.

Example 2.'62;g'rams of the azodyestuffsfrom diazotized 2,4 dichloroaniline 6 sulfonic acid and fl-naphthol are dissolved in 500 cos. of water at 95-100 C. Thereto are added 2 grams of copper sulfate and after the same have dissolvedz5 grams of calcined sodium carbonate; when the latter have dissolved, 20 grams of-sodlum sulfite free from water are introduced. After stirring for one hour at 95-100 0., the new dyestufihaving in the free state the following; formu1a:

is isolated in the usual manner. It dyes wool golden-yellow shades.

When substituting the 2,4-dichlo roaniline-6- sulfonic acid by 2-chloroaniline-5-sulfonic acid or 2,5-dichloroaniline-4-su1fonic acid and the B- naphthol by acylamino-naphthols; the process can be performed inthe same manner.

Example 3.-53.'7 grams "of the dyestuff-from diazotized 1-chloro-2-naphthylamineJi-sulfonic acid and 2-hydroxynaphthalene-7-sulfonic acid are dissolved in water; and thereto isadded-at85 C. a solution of 20 grams of crystallized copper sulfate in 100 ccs. of water. After the-addition of 20 grams of calcined soda and-20 grams of sodium sulfitefree from water, the mixtureis stirred for one hour at 85-90 C. The 'dyestufi having in the free state the following formula:

. l1alogen wherein R1 and Re stand for radicals of the-benzene, or naphthalene series, with a watersoluble sulfite in the presence of an agentyielding copperin an aqueousneutral'to alkaline mediunrat a process is carried out in an aqueous neutral to soda-alkaline medium at a temperature between about .70" .C.. andabout 100 C.

5. The process which comprises reacting upon an azo'dyestufi of thegeneral formula:

wherein R. stands for a radical of the naphthalene series, with a watersoluble sulfite in the presence ofan agentyielding copper in an aqueous neutral'to alkaline medium at a temperaturebetween about C. and about 100 C.

6. Process as claimed in claim 1, in which the process is carried out with. copper sulfate in sodaalkaline medium at a temperature between about 95 C. to about 100 C.

7. The process which comprises reacting upon an azodyestuff; of the formula:

withsodiumsulflte in the presence of copper sulfateand in an aqueous soda-alkaline medium at 8. Aspnewproducts azodyestufis of the general formula:

wherein R stands for a naphthalene radical, dyeing-woolgenerallyryellow fastnessa'properties.

9. .The ..dyestuif of the :following formula:

I SOzH dyeing wool golden-yellow shadesof good fastness properties.

a 4 DETLEFDELFS.

to redshades of good. 

